Insecticidal composition



- Patented Aug. 5, 1947,

INSECTICIDAL COMPOSITION Vernon E. Haury, El Ccrrito, Cali!., assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application July 17, 1944, Serial No. 545,400

' 13 Claims. (01. lea-24 This invention relates to new and novel compounds which are particularly suitable for killing noxious insects and the like. More specifically, th invention is concerned with insecticidal compositions containing N-cyclo-substituted cyclo-olefinic imines having the imino nitrogen linked between two ring carbon atoms.

Among the best known toxicants used in insecticidal compositions, particularly in household insecticides, are pyrethrum and rotenone. These' are both derived from plants grown in foreign countries and are therefore expensive and not always obtainable in desired quantities. Thus, many organic compounds which are more readily available in this country have been proposed as toxicants for insecticidal compositions. However, although many of these proposed compounds are relatively eilicient for momentarily incapacitating insects, they are relatively inefficient for killing insects. In addition to the desirability of high toxic action, for use in insecticides, particularly in household insecticides, the compounds must be light-stable, compatible with light parafllnic mineral oils, such as kerosene, and free from injurious effect and oilensive odor to human beings and tendency to stain walls, fabrics, etc.

It is an object of the present invention to provide an insecticidal composition which is highly toxic to insects but of low toxicity to man and to provide new insecticidal compositions which can be prepared from readily available domestic and inexpensive materials. A further object is to provide an improved insecticidal composition containing a fast-acting synthetic toxicant which 35 is stable toward light. A further object ofthis invention is to provide an activator fortoxic plant extracts, such as pyrethrum and derris resin or rotenone, in insecticidal compositions.

We have found that N-cyclo-substituted cycloolefinic imines having the imino nitrogen atom linked between two ring carbon atoms are particularly efiective and highly active insecticidal agents. These compounds may be represented by the general formula:

'R1C=NR2 wherein R represents a cyclo-oleflnic radical,

' which is preferably alkylated with other lower alkyl groups, especially at the 3,5 positions and particularly dialkylated at the same ring carbon, and R: as a cyclic radical, which may be alicyclic, either saturated or olefinic, aromatic, or heterocyclic. Thus, for example R10 may be butyl cyclohexyls, dimethyl cyclohexyls, trimethylcyclohexyls, such as 3,3,5-trimethylcyclohexyl, 4-isobutyl cyclohexyl, endomethylene cyclohexyls, etc., or less preferably aromatic groups, such as, for example, phenyl, methallyl phenyl, tolyl, xylyl, vinyl phenyl, butyl phenyls, 4-isobutyl phenyl, naphthyl, methyl naphthyl, crotonyl naphthyl, triallyl naphthyl, anthryl, etc.,'or heterocyclic radicals, such as pyridyl, sulfolanyl, methyl sulfolanyl, pyrrolyl, thioenyl, furyl, butyl carbothionyl, octyl carbothionyl, etc. In general, there may be included in the rings, for example, such atoms or groups as Also, N-cyclo-substituted cyclo-olefinic imines 1 other warm-blooded animals. Another object is 30 may'be used, which also have in the molecule one or more of the following groupszsulfo, amino, hydroxy carboxy, amido, mercapto, keto, ether, ester, lactone, lactam, ketal, acetal, halogen, halohydrin, epoxide, cyanohydrin, azo, diazo, thiazo, oxazo, thioether, thioimino, cyano, thiocyano, etc.

The preferred compound of the present class of compounds is N-(3,3,5-trimethylcyclohexyl) isophoronimine, which may also-be named N- (3,3,5-trimethylcyclohexyl) -3,3,5-trimethyl-2-cyclohexen-l-onimine.

The present imines may be prepared in any suitable manner, such as by catalytic dehydrogenation of the proper secondary amines, as disclosed in my copending application Serial No. 529,873, filed April 5, 1944. Therein, the desired imines are produced by contacting a secondary amine, wherein the -NH group is directly linked to two carbon atoms at least one of which is directly linked to a hydrogen atom, with a dehydrogenation catalyst at a dehydrogenation temperature, i. e., a temperature sufficiently elevated to effect the removal of a hydrogen atom from the said hydrogen-bearing carbon atom and another hydrogen atom from the contiguous nicyclopentenyl, methylcyclopentyls. amyl cyclotrogen atom, thereby causing the formation of a carbon-nitrogen double bond. Thus, for example, N-(3,3,5-trimethylcyclohexyl) isophoronamine is converted to N-(3,3,5-trimethylcyclohexyl) isophoronimine by contacting said secondary amine with a dehydrogenation catalyst, e. 3.. an active nickel catalyst, at a temperature of between 100" C. and about 500 C. i

The N-cyclo-substituted cyclo-oleflnic imines, either alone or in combination with other active or inactive substances, may be applied to plants, animals, fabrics and the like, by spraying, dusting, pouring, dipping, etc., in the form of concentratedv liquids, solutions, suspensions, dusting powders, and the like, containing such concentration of the active principle as is most suited for the particular purpose athand. They may be applied, for example, in the form of dilute solutions, in a suitable solvent or mixture of solvents, containing, for instance, petroleum distillate, lignite tar oils, paraflln oils, naphthenes, chlorinated hydrocarbons, such as dichloropropane, chlorinated ethers, ketones, such as acetone, fenchyl and bornyl alcohols, monoand poly-hydric alcohols, glycol ethers, or the like or mixtures thereof.

The present compounds may be advantageously used in combination with other insecticides or fungicides such as pyrethrum, derris resins, rotenone, nicotine, lime-sulphur, Bordeaux mixture, copper sulfate, copper carbonates, sulphur, mercury compounds, sodium, calcium and lead arsenates, iron sulfate, phenol, paradichlorobenzene, unsaturated chlorides, higher unsaturated amides, alkene sulfides, alkyl dithiocarbamates, thiuram sulfides, thiocyanates, thiocyano esters,

When solutions of the N-cyclo-substituted cyclo-oleflnic imine in odorless base kerosene are placedon fllterpaper and exposedto air, the liquid evaporates leaving substantially no stain behind, which feature is of particular advantage in household insecticides.

The present compounds may also be mixed with or absorbed by finely divided solid materials, such as wood flour, talc, clay, bentonite, sulphur, and carbon black, and used asdusting insecticides. v

Modified Feet-Grady tests were made with the N-cyclo-substituted cyclo-oleflnic imine of the present invention. The general test is fully described in the 1940 "Blue Book," published -by the publisher of "Soap and Sanitary Chemicals periodical, on pages 193 to 197, as the large group method. Briefly, the test as practiced consists of releasing 100 to 150 flies in an air-conditioned case 6 x 6 x 6 feet and spraying them with 6 ml. of insecticide. After 10 minutes exposure the number of flies which are incapacitated or knocked down is noted and all flies transferred to a cage and allowed to recuperate in freshair for 24 hours, when the dead flies are counted. For the purpose of this study the percentages knocked down at 10 minutes and kflled at 24 hours were recorded, as well as the official Peet- Grady numerical rating. The results obtained by testing in the above manner N -(3,3,5-trimethylcyclohexyl) isophoronimine in highly refined, odorless kerosene with and without added Pyrethrum and, for comparison, a closely related but much less effective compound in said kerosene are given in the following table:

' Per cent Per cent Per cent by vol. of Numerical Test No. 6% by vol. of Agent Pyrethmm knlgc 11:31am 2412mm Mug 1 Extract Di-(3.3,5-trimethylcyclohexyl) amine 0 47 i4 -23 N-(3,3,6-trimethy1cyclohexyl; isophoronimine. 0 95 63 +16 N-(3,3,6-trimethylcycloheryi isophoronimine. 5 95 79 +35 l The numerical rating is calculated as the difference in the percent 24 hour kill from that obtained with an odorless kerosene solution of 6% by vol. 01 202i pyrethrum extract concentrate.

As will be readily apparent, the most desirable 55 N-cyclo-substituted cyclo-oleflnic imine and solvent, or solvent mixture, or combination with other active and inactive ingredients, will depend considerably upon the particular use for which the material is intended.

For use in household insecticides, N-cyclo-substituted cyclo-olefinic imine is preferably dissolved in a light hydrocarbon oil such as highly refined, odorless kerosene or kerosene distillate with or without the addition of other insecticides and sprays. Ordinarily from about 1% to 25% and preferably from 2% to 8% of the present toxicants are used in such sprays.

For use in sprays, such as horticultural spray oils, there may be added emulsifying agents, such as partial esters of polyhydric alcohols, e. g. glycerol mono-oleate, poly'ethylene glycol mono laurate, palmitate, stearate, oleate, etc., various soaps, alkali metal salts of sulfuric acid mono esters and organic sulfuric acids and the like.

2. An insecticidal composition comprising a carrier and toxic agent having the general formula RiC N-Ra, wherein R10 represents an oleilnic alicyclic radical, and R2 is an alicyclic radical.

3. The process of eradicating insects, bacteria, and fungi comprising the step of exposing them to a toxic agent having the general formula R1C=NR2, wherein RiC represents an oleflnic alicyclic radical, and R2 is a cyclic radical selected from the group consisting of alicylic, aromatic, and heterocyclic radicals.

4. An insecticidal composition comprising a carrier and a toxic agent having the general formula RiC=NR:, wherein RiC represents an olefinic alicyclic radical, and R2 is an allwlated alicyclic radical.

5. An insecticidal composition comprising a carrier and toxic agent having the general formula R1C=NR2, wherein R represents an alkylated olefinic alicyclic radical, and R2 is a carbocyclic radical.

6. An insecticidal composition comprising a carrier and toxic agent having the general formula R1C=NR2, whereinR1C represents an alkylated alicyclo-olefinic radical, and R2 is an alkylated alicyclic radical. v

7. An insecticidal composition comprising a carrier and a polyalkylated cyclohexenyl imine wherein the imino nitrogen atom is directly attached to the ring of an alkylated alicyclic radical and has the imino nitrogen atom linked between two ring carbon atoms.

8. An insecticidal composition comprising a carrier and a 3,3,5-trimethyl cyclohexenyl imine wherein the imino nitrogen atom is directly attached to the ring of an alkylated alicyclic radical and has the imino nitrogen atom linked between two ring carbon atoms.

9. An insecticidal composition comprising an insecticidal plant extract and a toxic agent hav-.

ing the general formula R1C=NR2, wherein RiC represents an olefinic alicyclic radical, and R2 is a cyclic radical selected from the group Consisting of alicyclic, aromatic, and heterocyclic radicals.

10. An insecticidal composition comprising yrethrum and an N-cyclo-substituted cyclo-oleflnic imine having the lmino nitrogen atom linked between two ring carbon atoms.

11. A plant spray insecticide comprising a mineral spray oil, an emulsifying agent and a toxic agent having the general formula R1C=N-Rz,

wherein R1C represents an oleflnic alicyclic rad-.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,390,597 Law et a1 Dec. 11, 1945 2,045,574 Adkins June 30, 1936 2,198,375 Bruson Apr. 23, 1940 2,217,622 Lichty Oct. 8, 1940 2,239,491 Kuhn Apr. 22, 1941 2,307,482 Ballard et a1 Jan. 5, 1943 

